The present application pertains to fuel processors for providing hydrogen to fuel cells, and more particularly to the mixing of fuel and an oxidant for use in an autothermal reformer.
A fuel cell is an electrochemical device for continuously converting chemicalsxe2x80x94a fuel and an oxidant into direct-current electricity. It consists of two electronic-conductor electrodes separated by an ion-conducting electrolyte with provision for the continuous movement of fuel, oxidant, and reaction product into and out of the cell. Fuel cells differ from batteries in that electricity is produced from chemical fuels fed to them as needed, so that their operating life is theoretically unlimited. Fuel is oxidized at the anode (negative electrode), giving electrons to an external circuit. The oxidant accepts electrons from the anode and is reduced at the cathode. Simultaneously with the electron transfer, an ionic current in the electrolyte completes the circuit. The fuels range from hydrogen, and carbonaceous materials to redox compounds, alkali metals, and biochemical materials. Fuel cells based on hydrogen and oxygen have a significant future as a primary energy source. Cells of this type are under development for use as a power source for electric automobiles, the hydrogen being derived from methanol, gasoline, diesel fuel or the like.
Fuel cells such as PEM fuel cells, have been proposed for many applications including electrical power plants to replace internal combustion engines. PEM fuel cells are well known in the art and include a xe2x80x9cmembrane electrode assemblyxe2x80x9d (a.k.a. MEA) comprising a thin, proton transmissive, solid polymer membrane-electrolyte having an anode on one of its faces and a cathode on the opposite face. The solid polymer electrolytes are typically made from ion exchange resins such as perfluoronated sulfonic acid. The anode/cathode typically comprise finely divided catalytic particles (often supported on carbon particles) admixed with proton conductive resin. The MEA is sandwiched between a pair of electrically conductive elements which (1) serve as current collectors for the anode and cathode, and (2) contain channels for distributing the fuel cell""s gaseous reactants over the surfaces of the respective anode and cathode. In PEM fuel cells, hydrogen is the anode reactant (i.e. fuel) and oxygen is the cathode reactant (i.e. oxidant).
For vehicular applications it is desirable to use a carbon-bound hydrogenous fuel (e.g. methane, gasoline, methanol, etc.). Liquid such fuels are particularly desirable as the source of the hydrogen used by the fuel cell owing to their ease of on-board storage and the existence of a nationwide infrastructure of service stations that can conveniently supply such liquids. These fuels must be dissociated to release their hydrogen content for fueling the fuel cell. The dissociation reaction is accomplished in a so-called xe2x80x9cprimary reactorxe2x80x9d which is the first in a series of reactors comprise the fuel processor. Other reactors in the fuel processor serve to remove CO from the hydrogen produced by the primary reactor. One known such primary reactor for gasoline, for example, is a two stage chemical reactor often referred to as an xe2x80x9cautothermal reformerxe2x80x9d. In an autothermal reformer (ATR), gasoline and water vapor (i.e. steam) are mixed with air and pass sequentially through two reaction sections i.e. a first xe2x80x9cpartial oxidationxe2x80x9d (POX) section, and second a steam reforming (SR) section. In the POX section, and with an open flame or a catalyst, the gasoline reacts exothermically with a substoichiometric amount of air to produce carbon monoxide, hydrogen and lower hydrocarbons such as methane. The hot POX reaction products, along with the steam introduced with the gasoline, pass into a SR section where the lower hydrocarbons and a fraction of the carbon monoxide react with the steam to produce a reformate gas comprising principally hydrogen, carbon dioxide and carbon monoxide. The SR reaction is endothermic, but obtains its required heat either from the heat that is generated in the exothermic POX section and carried forward into the SR section by the POX section effluent, or from other parts of the fuel cell system (e.g. from a combustor). One such autothermal reformer is described in International Patent Publication Number WO 98/08771, published Mar. 5, 1998.
Downstream of the ATR, the carbon monoxide contained in the SR effluent is removed, or at least reduced to very low concentrations (i.e. less than about 20 ppm) that are non-toxic to the anode catalyst in the fuel cell. To this end, fuel processors are known that cleanse the SR effluent of CO by first subjecting it to a so-called xe2x80x9cwater-gas-shiftxe2x80x9d reaction (i.e. CO+H2Oxe2x86x92CO2+H2) followed by reacting it with oxygen (i.e. as air) in a so-called xe2x80x9cpreferential oxidation reaction (i.e CO+{fraction (1/20)}2xe2x86x92CO2). The CO-cleansed, H2-rich reformate is then supplied to the fuel cell.
It is highly desirable for effective operation of an ATR that the gaseous fuel and gaseous oxidant be mixed thoroughly before entering the POX section. It is also particularly important that the mixture not burn prematurely due to the presence of oxidant in the heated environment upstream of the POX. The present invention is directed towards improving the mixing of fuel and oxidant supplied to a POX reactor so as to eliminate premature burning or flashing of the mixture before it enters the POX reactor, and thereby eliminate the formation of carbon particles (i.e. soot) upstream of the POX.
It is an object of the present invention to provide a POX reactor having a mixing vessel at its inlet for mixing fuel and oxidant by introducing either fuel or oxidant into the vessel at a first location and then introducing the other fuel or oxidant at a second location sufficiently downstream of the first location that the mixture does not recirculate within the vessel, but rather proceeds directly to the vessel""s exit unburned. The fuel (or oxidant) exits the inlet from a plurality of closely-spaced tubes which extend well downstream of where the oxidant (or fuel) is introduced into the mixing vessel and in the direction of the POX reactor thereby decreasing the time that the gaseous fuel is exposed to the oxidant in the mixing vessel before the mixture passes into the POX reactor thereby substantially preventing premature burning of the fuel and consequent soot formation.
Described is apparatus for mixing fuel and an oxidant for supply to an ATR that provides hydrogen to a fuel cell. The apparatus comprises a mixing vessel having a first inlet for movement of gaseous fuel (or oxidant) therethrough and a second inlet for movement of gaseous oxidant (or fuel) therethrough, which inlets are spaced apart from each other in the direction of flow through the vessel and an exit spaced from the inlets and adjacent a POX reactor that partially combusts the mixture of fuel and oxidant exiting from the mixing vessel. The first inlet comprises a plate with a plurality of tubes extending therefrom through which the fuel or oxidant passes. The tubes extend into the mixing vessel so as to discharge fuel (or oxidant) downstream of the second inlet and near the exit of the vessel such that the fuel does not come into contact with the oxidant until the gaseous fuel (or oxidant) exits from the tubes thereby mixing the fuel with the oxidant in the gaseous state just prior to passing into the POX reactor (e.g. into the catalyst reaction bed of a catalytic POX reactor).
Also described is a method of mixing fuel and an oxidant in a vessel for supply to a POX reactor comprising mixing gaseous fuel and gaseous oxidant in the vessel by passing fuel or oxidant through a first inlet of the vessel; passing fuel or oxidant through a second inlet of the vessel, which inlets are spaced apart from each other and from an exit that is near a POX reactor that partially combusts the fuel-oxidant mixture exiting from the mixing vessel; wherein the first inlet is comprised of a plate with a plurality of tubes extending therefrom through which the fuel or oxidant passes; and wherein the tubes extend into the mixing vessel to near the exit of the vessel and discharge their gas downstream of the second inlet""s discharge points such that the fuel does not come into contact with the oxidant until the gaseous fuel or oxidant exits from the tubes thereby mixing the fuel with the oxidant in the gaseous state just prior to the fuel-oxidant mixture passes through the exit into the POX reactor.